Arsenic (III) oxide

Arsenic is a redirect to this article. For yellow arsenic see arsenic (III) sulfide . For red arsenic, see Realgar .

Crystal structure
__ As 3+      __ O 2−
General
Surname	Arsenic (III) oxide
other names	Arsenic trioxide Arsenic Arsenic anhydride Diarsenic trioxide
Ratio formula	As 2 O 3
Brief description	white, odorless solid
External identifiers / databases
CAS number 1327-53-3 EC number 215-481-4 ECHA InfoCard 100.014.075 PubChem 261004 ChemSpider 229103 DrugBank DB01169 Wikidata Q7739
Drug information
ATC code	L01 XX27
Drug class	Antineoplastic agent
properties
Molar mass	197.84 g mol −1
Physical state	firmly
density	3.74 g cm −3
Melting point	312.3 ° C
boiling point	465 ° C
solubility	37 g l −1 in water
safety instructions
Please note the exemption from the labeling requirement for drugs, medical devices, cosmetics, food and animal feed GHS hazard labeling from  Regulation (EC) No. 1272/2008 (CLP) , expanded if necessary danger H and P phrases H: 350-300-314-410 P: 201-280-301 + 310-330-303 + 361 + 353-304 + 340-310-305 + 351 + 338-308 + 313
Authorization procedure under REACH	of particular concern : carcinogenic ( CMR ); subject to approval
MAK	Switzerland: 0.1 mg m −3 (based on arsenic, measured as inhalable dust )
Toxicological data	10 mg kg −1 ( LD 50 ,  rat ,  oral )
Thermodynamic properties
ΔH f 0	−657.41 kJ mol −1
As far as possible and customary, SI units are used. Unless otherwise noted, the data given apply to standard conditions .

Arsenic (III) oxide , As ₂ O ₃ , also diarsentrioxide , (white) arsenic , from Latin arsenicum from ancient Greek ἀρσενιχόν , or (imprecisely) arsenic trioxide is the anhydride of the arsenic acid (H ₃ AsO ₃ ) that does not occur in the free state . Technically it is the most important chemical compound of arsenic . The oxide is also known as white arsenic and arsenicum album .

Historical use

Murder poison

Arsenic has long been notorious as a murderous poison. It has been by far the most widely used poison since late antiquity. The ironic French term poudre de succession (“inheritance powder”) for arsenic is derived from this use as a poison, as is the German term “old seat powder”. Many historical poisonous mixtures, such as Aqua Tofana, contained arsenic as an essential component. By taking small amounts regularly, the human organism does not get used to the poison, but the absorption through the mucous membrane is significantly reduced (so-called arsenic resistance) and the minimum lethal dose is higher, so that oral doses are tolerated that would be lethal for others. For this reason, some rulers regularly ingested small amounts of substances such as arsenic in order to protect themselves against poisoning attacks ( mithridatisation ). In ancient Latin texts, an assassination attempt on a prince, if one wanted to avoid bloodshed, is called coniuratio pulveraria , ie "a conspiracy with poison powder". Such an attack was made on Margrave Jakob III in 1590 perpetrated by Baden-Hachberg .

For centuries arsenic could not be detected chemically. If the murderer used the correct dose, known since the 16th century, the murder could hardly be proven to him. As recently as 1840, 90 to 95 percent of all poisoning could be traced back to the use of arsenic. After the Marsh Probe was introduced in 1836, the number of arsenic assassinations gradually decreased.

Pest Control

In addition to its high toxicity, a major reason why arsenic was used as a murderous poison was its easy accessibility. It was often used as insect , mouse and rat poison (e.g. in the form of “mouse butter”, i.e. fat with arsenic globules) and was available in various formulations in pharmacies. A well-known poisoner who poisoned 15 people in this way was Gesche Gottfried , who died on the scaffold in Bremen in 1831.

Corpse preservation

In the funeral services arsenic was (III) oxide since the late 18th century to the corpse preservatives used. In “arterial preservation”, the corpse was injected with a mixture of alcohol and arsenic into the bloodstream , mostly through the carotid artery . A corresponding method was described by the British physician William Hunter (1718–1783) and first used in practice in 1775 by his brother John (1728–1793). Since formaldehyde was discovered as a preservative in 1855 , arsenic (III) oxide lost its use in this area by the end of the 19th century.

drug

The stimulating effect of small doses of arsenic had been known for a long time. Especially in the 19th century there was the fashion of eating arsenic in certain areas (in Austria in Tyrol and Styria , as well as in the southern states of the USA) , in which arsenic was used as an intoxicant.

Horse trade

Arsenic was fraudulently given to horses by horse traders in order to make older, weaker animals appear healthier (" rosebushers "). This gave the horses a shiny coat and a "blooming" appearance.

Depilation

In ancient Rome, arsenic was also used as a depilation agent for pubic hair.

drug

In medieval ophthalmology , arsenic (from Latin arsenicum , white arsenic, arsenic trioxide, As ₂ O ₃ , or red arsenic, arsenic sulfide, AsS ₃ ) was a common component of eye wash recipes for red eyes or wing skin .

Occurrence

Arsenic trioxide is produced when elemental arsenic is burned in the air. In mineral form, arsenic occurs as a cubic arsenolite (arsenic flower) , consisting of As ₄ O ₆ molecules analogous to the structure of P ₄ O ₆ , and as a monoclinic claudetite .

Extraction and presentation

Technically, arsenic trioxide is obtained by roasting ores containing arsenic in so-called poison huts .

${\displaystyle \mathrm {2\ FeAsS+5\ O_{2}\longrightarrow Fe_{2}O_{3}+2\ SO_{2}+As_{2}O_{3}} }$

The arsenic trioxide escapes as volatile smelter smoke . The gas condenses into a white powder in long channels ( poison traps ). The raw product is cleaned by sublimation . Depending on the condensation temperature, you get a white powder, which is called poison meal , or the colorless, glass-like arsenic glass .

The production of pure arsenic trioxide from the crude product succeeds with the conversion to arsenic (III) chloride and its further hydrolysis.

${\displaystyle \mathrm {2\ AsCl_{3}+3\ H_{2}O\longrightarrow As_{2}O_{3}+6\ HCl} }$

properties

Arsenic trioxide comes as a white, odorless powder or as whitish porcelain-like pieces on the market. The substance is corrosive and carcinogenic .

Usage today

Arsenic trioxide is used to produce poisons against rodents and insects as well as to preserve pelts and hides (→ taxidermy ). In glass production it is used to refine and decolorize the melt.

In addition, arsenic trioxide has been known as an effective agent for blood diseases and syphilis since ancient times . In Europe today it has the status of an orphan drug and is used under the trade name Trisenox (manufacturer Cephalon ) for the treatment of acute promyelocytic leukemia (APL), a subtype of acute myeloid leukemia .

It is also used as Arsenicum album in homeopathy .

Arsenic trioxide is a basic titer substance according to the pharmacopoeia .

safety instructions

The substance has been included in the candidate list of substances of very high concern (SVHC).

toxicity

Arsenic trioxide

Arsenic trioxide is a strong poison and clearly carcinogenic . Less than 0.1 g ingested orally can be fatal. The poison effect is based on the disruption of several processes. Among other things, the build-up of energy-rich phosphorus compounds and thus the energy metabolism is inhibited. Several intracellular signal transmission paths and enzymes as well as transport processes on the membranes are disturbed by inactivation of receptors. The inhibition of repair mechanisms and the inactivation of so-called tumor repressor proteins are responsible for the carcinogenic effect. Acute poisoning manifests itself after a few hours as massive diarrhea and vomiting. There is also severe pain, initially in the gastrointestinal area, later, after an apparent improvement, cramps occur in the extremities. The physical weakness increases steadily, clouding of consciousness, visual disturbances and slow cooling down can already be registered one day before the onset of death. At the autopsy one finds u. a. Pea- to bean-sized stomach erosions on the back wall of the stomach, where the poison crystals had stuck to the mucous membrane.

To prevent accidents, work under a hood when handling this connection. As a countermeasure in the event of poisoning, rinse the mouth, induce vomiting (not in unconscious persons) and immediately notify a doctor.

Despite its high toxicity, arsenic was also used as a stimulant by arsenic eaters in the 19th century (see above). The tolerance that develops is not based on the body getting used to arsenic trioxide, but solely on the reduced absorption through the mucous membranes.

proof

The arsenic contained in arsenic trioxide can be detected, for example, with the help of Marsh's sample , which, however, is also positive for antimony . A more suitable quantitative detection method is, for example, mass spectrometry with inductively coupled plasma (ICP-MS) or atomic absorption spectroscopy (AAS).

Web links

Wiktionary: Arsenik  - explanations of meanings, word origins, synonyms, translations

• Arsenicum. In: Johann Heinrich Zedler : Large complete universal lexicon of all sciences and arts . Volume 2, Leipzig 1732, column 1652-1654.
• Lecture Uni-Kiel (PDF; 412 kB)

Individual evidence

1. ↑ ^{a b c d e f} data sheet arsenic (III) oxide from AlfaAesar, accessed on February 7, 2010 ( PDF )(JavaScript required) .
2. ↑ ^{a b} Entry on arsenic (III) oxide in the GESTIS substance database of the IFA , accessed on February 1, 2016(JavaScript required) .
3. ↑ Entry on Diarsenic trioxide in the Classification and Labeling Inventory of the European Chemicals Agency (ECHA), accessed on February 1, 2016. Manufacturers or distributors can expand the harmonized classification and labeling .
4. ↑ ^{a b} Entry in the SVHC list of the European Chemicals Agency , accessed on July 15, 2014.
5. ↑ Entry in the register of substances subject to authorization of the European Chemicals Agency , accessed on July 15, 2014.
6. ↑ Swiss Accident Insurance Fund (Suva): Limit values ​​- current MAK and BAT values (search for 1327-53-3 or arsenic (III) oxide ), accessed on October 24, 2016.
7. ^ AF Holleman , E. Wiberg , N. Wiberg : Textbook of Inorganic Chemistry . 91st – 100th, improved and greatly expanded edition. Walter de Gruyter, Berlin 1985, ISBN 3-11-007511-3 , p. 675.
8. ^ Schneider, Johann Gottlob; Passow, Franz: Concise dictionary of the Greek language . Second edition revised and enlarged with prosodic tables. tape 1 . Vogel, Friedrich Christian Wilhelm, Leipzig 1826, urn : nbn: de: bvb: 12-bsb10523497-9 .
9. ^ Johannes Fecht : Historia colloquii Emmendingensis , Rostock 1694, p. 372.
10. ↑ Tom Hickman, Death - A User's Guide , London 2002, pp. 100-101.
11. ↑ Bettina Eva Stumpp: Prostitution in Roman antiquity . de Gruyter, 2001, ISBN 3-05-007755-7 , p. 91.
12. ↑ Jürgen Martin: The 'Ulmer Wundarznei'. Introduction - Text - Glossary on a monument to German specialist prose from the 15th century. Königshausen & Neumann, Würzburg 1991 (= Würzburg medical-historical research. Volume 52), ISBN 3-88479-801-4 (also medical dissertation Würzburg 1990), p. 113 (“ainen stain haysset arsenicum that is right”).
13. ↑ Gundolf Keil : "blutken - bloedekijn". Notes on the etiology of the hyposphagma genesis in the 'Pommersfeld Silesian Eye Booklet' (1st third of the 15th century). With an overview of the ophthalmological texts of the German Middle Ages. In: Specialized prose research - Crossing borders. Volume 8/9, 2012/2013, pp. 7–175, here: p. 9.
14. ↑ G. Brauer (Ed.): Handbook of Preparative Inorganic Chemistry 2nd ed., Vol. 1, Academic Press 1963, pp. 600-601.
15. ↑ Entry on arsenic. In: Römpp Online . Georg Thieme Verlag, accessed on September 30, 2016.
16. ^ Avoxa media group Deutscher Apotheker GmbH: Arsenic trioxide | Trisenox® | 86 | 2002. Retrieved October 19, 2019 . 
17. ↑ Dietmar P. Berger, Rupert Engelhardt, Roland Mertelsmann : The Red Book: Hematology and Internal Oncology. 4th edition. Hüthig Jehle Rehm, 2011, ISBN 978-3-609-51216-7 , p. 120 ( limited preview in the Google book search).
18. ↑ Federal Environment Agency: Arsenic compounds . Retrieved September 16, 2012.

This article is about a health issue. It is not used for self-diagnosis and does not replace a diagnosis by a doctor. Please note the information on health issues !